JPH0733009B2 - How to save ruins and remains - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving ruins / remains, and more particularly to a method for preserving ruins / remains by using a polyalkylene glycol-added silicone compound or a silicone-based curable composition in combination.

[0002]

[Prior Art] People have lived in the Japanese archipelago for tens of thousands of years, and there are dwellings from the Jomon and Yayoi eras to the modern times, agricultural land, graves, shell mounds, temples, and tatara traces. Ware, copper mirror,
Many ruins and remains are left, such as the foundry sites of castings.
These ruins and remains are valuable cultural assets left by our ancestors, and it is strongly desired to preserve them in their original form in order to preserve and utilize them in the future without their destruction. The ruins and remains so far are paddy fields, wilderness, forests,
It has been buried underground in lakes, rivers, etc. and protected by its soil and water. Therefore, even after a long period of several thousand years, it has retained its original shape in good condition.

However, in recent years, because of the construction of roads, houses, factories, playgrounds, stores, cultivated land, etc. due to the improvement of social infrastructure, the opportunity to dig up the ground has increased, and many new archaeological sites have been discovered. If the remains / remains that have been dug up are left as they are, weathering due to wind and rain, shrinkage cracks due to changes in soil water, overgrowth of plants and moss, and destruction by humans will cause the original shape to disappear rapidly, which is a major problem for preservation and utilization. Has become.

[0004] For the purpose of preserving the ruins and exhibiting them for display, so-called archaeological halls, etc. have been constructed in which the entire ruins are covered with a protection building and visitors observe through the glass windows. As a result, the effects of wind and rain and destruction by humans and animals have disappeared, but mold and moss grow on the surface of the ruins, causing insects that feed on them and causing damage to the ruins and remains. ing. As a countermeasure against this, a biocontrol agent such as formalin water or gramxone was sprayed about once a month, but it has little effect of preventing biological damage and has an effect on the human body. Therefore, a new biological control method is desired. On the other hand, preservation by the protection building of the ruins is due to evaporation of soil moisture due to greenhouseization (20
About 800 cc of water evaporates per 1 m ² / day at around ℃), and ruins are dried and cracks occur, and some of them are desertified. In addition, there are some inconveniences such as the inability to distinguish the burned soil from the furnace due to drying etc., the precipitation of soluble salts in a part of the ruins due to evaporation of soil moisture, and the cracking and collapse of the remains. is there.
As a countermeasure against these, polyethylene glycol, acrylamide, magnesium acrylate, vinyl acetate emulsion, etc. have been used to protect the ruins by forming a protective film on the surface. However, polyethylene glycol was fairly stable for about a week after the treatment, but after that it dissolved in the soil water and diffused, and the effect was lost within a few weeks. Acrylamide contracted as the gelled protective film dried. There is a problem that it is raised, and the soil surface is peeled off to peel up into scales, and magnesium acrylate also deteriorates over time and peels off into scales.

[0005]

DISCLOSURE OF THE INVENTION The present invention is to prevent mold and moss from being generated on the surface of ruins and remains, and in addition, to peel off the soil surface of the ruins or to generate cracks, The task was to provide a method for preserving archaeological sites / remains that can prevent desertification, prevent changes in color tone, keep treatment effects for a long time, and have no adverse effects on the human body. It is a thing.

[0006]

As a result of earnest research, the present inventors have conducted tests on many low molecular weight compounds and high molecular weight compounds and combinations thereof, and in the case of specific silicone compounds and combinations thereof, The present invention has been completed by demonstrating that the above problem can be solved.

That is, according to the present invention, the following formula (Formula 2) is applied to the surface of the ruins / remains:

[Chemical 2] (In the formula, m is 0 to 10, n is 1 to 10, x is 2 to 6, y
Is 3 to 10, z is 0 to 10, A is -H, -C.
_{H 3, -C 2 H 5,} -C 3 H 7, -COCH 3 and -
It represents a group selected from COC ₂ H ₅ . ) Soil polyalkylene glycol adducts silicone compound represented by the Rights
The present invention relates to a method for preserving ruins / remains, which is characterized by being sprayed at a rate of 100 to 3000 g per 1 m ^{2 of} surface .

A preferred embodiment of the method for preserving ruins and remains of the present invention is the combined use of the above-mentioned polyalkylene glycol-added silicone compound and a silicone-based curable composition.

In the present invention, the surface of the ruins / remains means a dwelling site from the Jomon period / Yayoi period to the modern times, a farmland site, a tomb site, a shell mound, a temple site, a tatara site, a pottery, a copper mirror, a casting, etc. It mainly means the surface of the soil that constitutes the site of the manufacturing plant.

The polyalkylene glycol-added silicone compound used in the present invention is represented by the above general formula, for example, the following chemical formulas (Formula 3 to 8).

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

In the present invention, the polyalkylene glycol-added silicone compound mainly plays a role of preventing the generation of mold and moss. The polyalkylene glycol-added silicone compound itself is a known compound, and its use as a surface tension lowering agent has been known so far, but the effect of preventing the generation of mold and moss on the soil surface as in the present invention. Has never been reported, and this property was first discovered in the present invention.

In the present invention, in order to spray the polyalkylene glycol-added silicone compound on the soil surface of the ruins / remains, it is desirable to dissolve the compound in water, alcohols and organic solvents and carry out by air spray method. In addition, it is desirable that this spraying be performed uniformly on the soil surface.
The amount of polyalkylene glycol-added silicone compound applied to the soil surface is 100 to 3000 g / soil surface 1
A ratio of m ² is desirable. If the amount is 100 g / m ² or less, there is no effect of preventing the formation of mold and moss, and 3000 g
Even if the spray amount is increased by more than / m ^{2, the} effect reaches the saturation point and is not economical.

Next, the case where the polyalkylene glycol-added silicone compound and the silicone-based curable composition are used in combination will be described. The use of polyalkylene glycol-added silicone compounds alone prevents the growth of mold and bryophytes, but this is not limited to the case where archaeological sites and archaeological sites are preserved in good condition. , Even if there is a protective building, the water content in the soil is too high or too low, the temperature and humidity of the outside air are too high or too low, and there is a case where wind and rain directly affect it or humans and animals come into direct contact with it. In some cases, these protective films are required. A silicone-based curable composition is used together as the protective film forming agent. Examples of the silicone-based curable composition include the following. Example 1 The following formula: R ¹ _n Si (OR ² ) _4-n (wherein R ¹ represents a methyl group, an ethyl group, an amyl group, a phenyl group or a vinyl group, and R ² represents a methyl group, an ethyl group, a propyl group. Represents a group, a butyl group or an acetyl group, n
Represents an integer of 1 to 3) and at least 1 of organoalkoxysilane or organoacetoxysilane
After dissolving the seed in an acidic or neutral aqueous solution, at least one of lithium silicate and other silicate compounds is added and dissolved in the aqueous solution, and the aqueous solution is adjusted to have an alkaline pH of 11 to 12, A solution prepared by adding an oxide, the details of which are disclosed by the present inventors.
No. 7974. Example 2 0.3 to 30 parts by weight of a crosslinking agent (tetraethyl silicate, tetrapropyl silicate, etc.), a curing catalyst (dibutyl tin laurate) based on 100 parts by weight of a hydroxylated diorganopolysiloxane having two or more hydroxyl groups in the molecule. Of dicarboxylic acid such as dibutyltin diacetate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin dipalmitate, dioctyltin distearate, tin laurate, tin octylate, iron octylate, lead octylate, tetrabutyl titanate 0.01 to 8 parts by weight of a metal salt, an amine compound such as n-hexylamine or guanidine, or a hydrochloride thereof, etc. is added to the composition.
Water, alcohols, fibers, inorganic powders, oily ingredients and the like may be added. Example 3 Crosslinking agent (hydrogenated diorganopolysiloxane having two or more Si—H groups in the molecule) 20 per 100 parts by weight of vinylated diorganopolysiloxane having two or more vinyl groups in the molecule To 100 parts by weight, and 0.001 to 3 parts by weight of a curing catalyst (chloroplatinic acid, platinum black, platinum asbestos, platinum silica gel, platinum activated carbon, potassium chloroplatinate, etc.) are added. Surfactants, water, alcohols, fibers, inorganic powders, organic solvents, oily components and the like may be added. Examples of surfactants: polyoxyethylene octyldodecyl alcohol, polyoxyethylene 2-decyl tetradecyl alcohol, polyoxyethylene oleyl alcohol ether, sorbitan monooleate, sorbitan monolaurate, polyoxyethylene sorbitan monooleate, glyceryl monooleate. Oleate, glyceryl monomysterate, polyoxyethylene glyceryl monooleate, polyoxyethylene dihydrocholesterol ether, polyoxyethylene octylphenol ether, glycerol monoisostearyl ether, polyoxyethylene glycerol monoisostearate, diglyceryl monostearate , Decaglyceryl decasterate; potassium of higher fatty acids such as myristic acid, stearic acid, and oleic acid Beam, sodium, diethanolamine, triethanolamine, salts of amino acids and the like; particularly diorganopolysiloxane - polyoxyalkylene copolymer. Examples of alcohols: ethanol, butanol, ethylene glycol, polyethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dipropylene glycol, polypropylene glycol, glycerin, diglycerin, triglycerin, tetraglycerin, Glucose, maltose, maltose, sucrose, fructose, xylitose, sorbitol and the like. Examples of fibers: microcrystalline cellulose, silk fibroin, fibroin powder, silk, cotton, wool, nylon, polyester, vinylon and other short fibers. Examples of inorganic powders: silicic acid anhydride, magnesium silicate, talc, kaolin, mica, titanium mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate,
Yellow iron oxide, Gunjou, carbon black, calamine, etc. Examples of organic solvents: benzene, toluene, xylene, isopropyl alcohol, ethylene glycol acetate, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, isopropyl acetate, ethyl acetate, butyl acetate, diisopropyl ketone, ethylene glycol diacetate, dimethyl ether and the like. Examples of oily ingredients: beef tallow, squalane, olive oil, evening primrose oil, rice bran oil, hydrocarbons, liquid paraffin, etc.

When the polyalkylene glycol-added silicone compound and the silicone-based curable composition are used in combination in the present invention, the polyalkylene glycol-added silicone compound may be sprayed first and then the silicone-based curable composition. Alternatively, both may be sprayed as a mixed solution, or the silicone-based curable composition may be sprayed first and then the polyalkylene glycol-added silicone compound.

[0015]

EXAMPLES The present invention will now be described based on examples.
The present invention is not limited to these. In addition, all the tests in the following examples were carried out at a pit dwelling site from Jomon period to Kofun period located at 4-11-22 Okamura, Isogo-ku, Yokohama. Example 1 The moss growing on the surface of the remains was carefully removed so as not to damage the surface of the remains, and the surface of the remains was cleaned with a soft brush to expose a fresh surface layer. Chemical 9):

[Chemical 9] A polyalkylene glycol-added silicone compound represented by the following was prepared as a 10% aqueous solution, and sprayed at 2000 g / m ² using a hand spray gun. After one week in the untreated area, moss was generated on the surface of the remains and turned a light green color, but in the area subjected to the above treatment, no moss was observed. As a result of observing changes with time in the treated parts, no moss and mold were found even after 2 years.

Comparative Example 1 When the amount of the polyalkylene glycol-added silicone compound sprayed in Example 1 was set to 50 g / m ² , generation of bryophytes and mold was recognized after one and a half years.

Example 2 When the amount of the polyalkylene glycol-added silicone compound applied in Example 1 was set to 100 g / m ² , 2
Even after a year, no moss or mold was found.

Example 3 Instead of the polyalkylene glycol-added silicone compound in Example 1, the following formula
0-12):

[Chemical 10]

[Chemical 11]

[Chemical 12] When the same test as in Example 1 was carried out using the compound represented by the formula (2), no moss and mold were found on the surface of the remains after two years.

Example 4 To 78 parts of water, 4 parts of methyltrimethoxysilane was slowly added with stirring, and when the aqueous solution became uniform and transparent, 12 parts of lithium silicate and 2 parts of sodium silicate were added and uniformly added. Stir until it becomes dry, then p with sodium hydroxide.
The H was adjusted to 12. Furthermore, 2 parts of aluminum oxide is added to form a uniform transparent liquid (silicone-based curable composition).
Got On the other hand, after the polyalkylene glycol-added silicone compound was sprayed on the surface of the remains in the same manner as in Example 1, the transparent liquid was sprayed at a rate of 1000 ml / m ² . After two years, no moss or mold was found on the surface of the remains, and no influence of rainfall or wind was found. Further, the shrinkage of the protective film did not damage the surface of the remains.

Example 5 Hydroxylated dimethyl polysiloxane (molecular weight 300
00) 40 parts by weight, polyethylene glycol (molecular weight 4
000) 5 parts by weight, stearic acid 2 parts by weight, polyoxyethylene sorbitan stearate 3 parts by weight, water 200 parts by weight, tetraethyl silicate 5 parts by weight, dibutyltin dilaurate 0.7 parts by weight, and further mixed by the following formula: 13):

[Chemical 13] 40 parts by weight of the compound represented by the formula (1) were added and mixed by stirring to prepare a treatment liquid (a mixed liquid of a polyalkylene glycol-added silicone compound and a silicone-based curable composition). In the same manner as in Example 1, 3000 ml /
It was sprayed at a rate of m ² . After two years, no moss or mold was found on the surface of the remains, and no influence of rainfall or wind was found. Further, the shrinkage of the protective film did not damage the surface of the remains.

Example 6 Vinylated dimethyl polysiloxane (molecular weight 20000)
30 parts by weight, polyoxyethylene octyldodecyl alcohol 6 parts by weight, glycerin monostearate 3 parts by weight, water 100 parts by weight, glycerin 3 parts by weight, hydrogenated dimethylpolysiloxane (molecular weight 8000) 15 parts by weight, platinum silica gel 0.6 By weight, 5 parts by weight of petrolatum were mixed by stirring to obtain a treatment liquid (silicone-based curable composition). On the other hand, the following formula (Formula 1
4):

[Chemical 14] After the compound represented by the formula (1) was sprayed at a rate of 1500 g / m ² , the treatment solution was sprayed at a rate of 500 ml / m ² .
After two years, no moss or mold was found on the surface of the remains, and no influence of rainfall or wind was found.
Further, the shrinkage of the protective film did not damage the surface of the remains.

[0022]

As described in detail above, the present invention is
By treating the surface of the ruins / remains with a polyalkylene glycol-added silicone compound that is harmless to the human body, it is possible to prevent the generation of moss and mold and preserve the ruins / remains in their original form. Is.

Further, by using this silicone compound in combination with a silicone-based curable composition, the retaining effect of the silicone compound is enhanced and the moss and mold preventing effect is maintained for a long period of time. The invention also makes it possible to protect the surface from physical and chemical effects. Moreover, the surface of the ruins / remains is not damaged by the expansion and contraction of the protective film itself by the silicone-based curable composition.

Claims (2)

[Reference number] C173 [Claims] 1. The following formula (Formula 1) on the surface of the ruins / remains: [Formula 1] (In the formula, m is 0 to 10, n is 1 to 10, x is 2 to 6, y
Is 3 to 10, z is 0 to 10, A is -H, -C.
_{H 3, -C 2 H 5,} -C 3 H 7, -COCH 3 and -
It represents a group selected from COC ₂ H ₅ . ) Soil polyalkylene glycol adducts silicone compound represented by the Rights
A method for preserving ruins / remains, characterized by spraying at a rate of 100 to 3000 g per 1 m ^{2 of} surface . 2. The method for preserving archaeological remains according to claim 1, wherein the polyalkylene glycol-added silicone compound according to claim 1 and the silicone-based curable composition are used in combination.